EP0932595A1 - Entfernung von carbonylverunreinigungen aus einem carbonylierungsverfahrensstrom - Google Patents
Entfernung von carbonylverunreinigungen aus einem carbonylierungsverfahrensstromInfo
- Publication number
- EP0932595A1 EP0932595A1 EP96932977A EP96932977A EP0932595A1 EP 0932595 A1 EP0932595 A1 EP 0932595A1 EP 96932977 A EP96932977 A EP 96932977A EP 96932977 A EP96932977 A EP 96932977A EP 0932595 A1 EP0932595 A1 EP 0932595A1
- Authority
- EP
- European Patent Office
- Prior art keywords
- phase
- acetic acid
- stream
- carbonylation
- iodide
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C53/00—Saturated compounds having only one carboxyl group bound to an acyclic carbon atom or hydrogen
- C07C53/08—Acetic acid
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C51/00—Preparation of carboxylic acids or their salts, halides or anhydrides
- C07C51/42—Separation; Purification; Stabilisation; Use of additives
- C07C51/487—Separation; Purification; Stabilisation; Use of additives by treatment giving rise to chemical modification
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C51/00—Preparation of carboxylic acids or their salts, halides or anhydrides
- C07C51/10—Preparation of carboxylic acids or their salts, halides or anhydrides by reaction with carbon monoxide
- C07C51/12—Preparation of carboxylic acids or their salts, halides or anhydrides by reaction with carbon monoxide on an oxygen-containing group in organic compounds, e.g. alcohols
Definitions
- This invention relates to a novel process for the purification of acetic acid formed by the carbonylation of methanol in the presence of a Group VIII metal carbonylation catalyst. More specifically, this invention relates to a novel process for reducing or removing carbonyl impurities from acetic acid formed by Group VIII metal-catalyzed, carbonylation processes.
- the carbonylation catalyst comprises rhodium, either dissolved or otherwise dispersed in a liquid reaction medium or else supported on an inert solid, along with a halogen-containing catalyst promoter as exemplified by methyl iodide.
- the rhodium can be introduced into the reaction system in any of many forms, and it is not relevant, if indeed it is possible, to identify the exact nature ofthe rhodium moiety within the active catalyst complex.
- the nature ofthe halide promoter is not critical.
- the patentees disclose a very large number of suitable promoters, most of which are organic iodides. Most typically and usefully, the reaction is conducted with the catalyst being dissolved in a liquid reaction medium through which carbon monoxide gas is continuously bubbled.
- the invention therein resides primarily in the discovery that catalyst stability and the productivity of the carbonylation reactor can be maintained at surprisingly high levels, even at very low water concentrations, i.e. 4 weight (wt) % or less, in the reaction medium (despite the general industrial practice of maintaining approximately 14 wt % or 15 wt % water) by maintaining in the reaction medium, along with a catalytically-effective amount of rhodium, at least a finite concentration of water, methyl acetate and methyl iodide, a specified 4 improved permanganate time and is substantially free from carbonyl impurities.
- vent gas from the splitter column overhead receiver decanter (which contains a portion of the condensed splitter column overhead gases) contains a substantial concentration of acetaldehyde and if this vent gas is further condensed and the condensate containing the high concentration of acetaldehyde is treated with an amino compound to remove the 15 carbonyl compounds therefrom, the inventory of acetaldehyde throughout the carbonylation reaction system is even more greatly reduced.
- the condensate from the vent gas is treated directly with an amino compound to remove carbonyl impurities.
- the condensate is combined with a small slipstream from the condensed splitter column overhead to be treated with an amino compound to remove the carbonyl compounds.
- the inventory of carbonyl compounds including acetaldehyde is greatly reduced by treating only minor amounts ofthe production streams ofthe carbonylation process, achieving greatly improved product quality and, at the same time, accomplishing such product quality without substantially increasing the cost of production.
- a feed of methanol is carbonylated in a liquid phase carbonylation reactor. Separation of products is achieved by directing the contents ofa reactor to a flasher wherein the catalyst solution is withdrawn as a base stream and recycled to the reactor while the vapor or volatile overhead which comprises largely the product acetic acid along with methyl iodide, methyl acetate, and water is directed to a methyl iodide-acetic acid splitter column.
- the overhead from the splitter column comprises mainly organic iodides, methyl acetate, acetic acid, and water, whereas from near the base ofthe splitter column is drawn the crude acetic acid which is usually directed to further purification by finishing distillation.
- the overhead from the splitter column containing the organic iodides is recycled to the carbonylation reactor. It was discovered that the carbonyl impurities present in the acetic acid product generally concentrate in the overhead from the splitter column.
- the splitter column overhead is treated with a compound i.e.. hydroxylamine which reacts with the carbonyl compounds to allow such carbonyls to be separated from the remaining overhead by means of distillation. Modified by such a treatment, the carbonylation of methanol yields an acetic acid product which has greath 6
- the liquid reaction medium employed may include any solvent compatible with the catalyst system and may include pure alcohols, or mixtures of the alcohol feedstock and/or the desired carboxylic acid and/or esters of these two compounds.
- the preferred solvent and liquid reaction medium for the low water carbonylation process comprises the carboxylic acid product.
- the preferred solvent is acetic acid.
- the desired reaction rates are obtained even at low water concentrations by including in the reaction medium methyl acetate and an additional iodide ion which is over and above the iodide which is present as a catalyst promoter such as methyl iodide or other organic iodide.
- the additional iodide promoter is an iodide salt, with lithium iodide being preferred. It has been found that under low water concentrations, methyl acetate and lithium iodide act as rate promoters only when relatively high concentrations of each of these components are present and that the promotion is higher when both of these components are present simultaneously (U.S. Pat. 5,001.259).
- the concentration of lithium iodide used in the reaction medium of the preferred carbonylation reaction system is believed to be quite high as compared with what little prior art there is dealing with the use of halide salts in reaction systems of this sort.
- the absolute concentration of iodide ion content is not a limitation on the usefulness of the present invention, only on the improvements in acetic acid production.
- the carbonylation reaction of methanol to acetic acid product may be carried out by contacting the methanol feed, which is in the liquid phase, with gaseous carbon monoxide bubbled through a liquid acetic acid solvent reaction medium containing the rhodium catalyst, methyl iodide-type promoter, methyl acetate, and additional soluble iodide salt promoter, at conditions of temperature and pressure suitable to form the carbonylation product.
- Figure 1 illustrates a carbonylation reaction process and acetic acid recovery system as modified to provide for the inco ⁇ oration ofthe present invention.
- Figure 2 illustrates a preferred embodiment for the removal of carbonyl impurities form acetic acid formed by a carbonylation reaction.
- the purification process of the present invention is useful in any process used to carbonylate methanol to acetic acid in the presence of a Group VIII metal catalyst such as rhodium and an iodide promoter.
- a particularly useful process is the low water rhodium catalyzed carbonylation of methanol to acetic acid as exemplified in aforementioned U.S. Patent No. 5,001,259.
- the rhodium component of the catalyst system is believed to be present in the form of a coordination compound of rhodium with a halogen component providing at least one ofthe ligands of such coordination compound.
- the rhodium component of the catalyst system may be provided by introducing into the reaction zone rhodium in the form of rhodium metal, rhodium salts and oxides, organic rhodium compounds, coordination compounds of rhodium, and the like.
- the halogen promoting component of the catalyst system consists of a halogen compound comprising an organic halide.
- alkyl, aryl, and substituted alkyl or aryl halides can be used.
- the halide promoter is present in the form of an alkyl halide in which the alkyl radical corresponds to the alkyl radical ofthe feed alcohol which is carbonylated.
- the halide promoter will comprise methyl halide, and more preferably methvl iodide. 8 prevent buildup of gaseous by-products and to maintain a set carbon monoxide partial pressure at a given total reactor pressure.
- the temperature of the reactor is controlled automatically, and the carbon monoxide feed is introduced at a rate sufficient to maintain the desired total reactor pressure.
- Liquid product is drawn off from carbonylation reactor 10 at a rate sufficient to maintain a constant level therein and is introduced to flasher 12 via line 1 1.
- the catalyst solution is withdrawn as a base stream 13 (predominantly acetic acid containing the rhodium and the iodide salt along with lesser quantities of methyl acetate, methyl iodide, and water), while the overhead 15 ofthe flasher comprises largely the product acetic acid along with methyl iodide, methyl acetate, and water.
- Dissolved gases in stream 1 1 consisting of a portion of the carbon monoxide along with gaseous by-products such as methane, hydrogen, and carbon dioxide exit the flasher through stream
- the overhead 20 from methyl iodide, acetic acid splitter column comprising mainly methyl iodide and methyl acetate plus some water, acetic acid and volatiles is normally recycled via line 21 to the carbonylation reactor 10.
- the product acetic acid drawn from the side of methyl iodide-acetic acid splitter column 14 near the base is directed via line 17 for final purification, such as to remove water, as desired, by methods which are known to those skilled in the art including, most preferably, distillation.
- the heavy phase 30 is comprised mainly of methyl iodide plus some methyl acetate and acetic acid as well as the alkane and carbonyl impurities.
- the light phase 32 is comprised mainly of water and acetic acid plus some methyl acetate and carbonyl impurities.
- a slip stream portion of the heavy phase 30 from methyl iodide-acetic acid splitter may then be subject to treatment and the remaining stream can be combined with the light phase 32 and with recycle products from other further purification processes containing methyl iodide, methyl acetate, water, and other impurities to become recycle 21.
- the iodide salt can be a salt with an organic metal or quaternary cation or inorganic cation.
- the iodide is added as metal salt, preferably it is an 5 iodide salt of a member of the group consisting of the metals of Group la and Group Ha of the periodic table as set forth in the "Handbook of Chemistry and Physics" published by CRC Press. Cleveland, Ohio, 1975-76 (56th edition).
- alkali metal iodides are useful, with lithium iodide being preferred.
- the additional iodide over and above the organic iodide promoter is present in the catalyst solution in o amounts of from about 2 to about 20 wt %, the methyl acetate is present in amounts of from about
- methyl iodide is present in amounts of from about 5 to about 20 wt %.
- the rhodium catalyst is present in amounts of from about 200 to about 1000 parts per million (ppm).
- Typical reaction temperatures for carbonylation will be approximately 150 to about 250°C, s with the temperature range of about 180 to about 220°C being the preferred range.
- the carbon monoxide partial pressure in the reactor can vary widely but is typically about 2 to about 30 atmospheres, and preferably, about 3 to about 10 atmospheres. Because ofthe partial pressure of by-products and the vapor pressure ofthe contained liquids, the total reactor pressure will range from about 15 to about 40 atmospheres.
- FIG. 1 A typical reaction and acetic acid recovery system which is used for the iodide-promoted rhodium catalyzed carbonylation of methanol to acetic acid is shown in Figure 1 and comprises a liquid-phase carbonylation reactor 10, flasher 12, and a methyl iodide-acetic acid splitter column 14 which has an acetic acid side stream 17 which proceeds to further purification.
- the carbonylation reactor 10 is typically a stirred vessel within which the reacting liquid contents are maintained 5 automatically at a constant level.
- the reaction of carbonyl impurities with hydroxylamine to form oximation products and the corresponding sulfate salts takes place in reactor 74.
- the oximation and salt products are soluble in the aqueous phase ofthe reactor provided adequate temperature and/or water concentration are maintained. To ensure formation ofthe oximation products, intimate contact and mixture ofthe carbonyl impurities and hydroxylamine is recommended.
- the reactor may be of any suitable equipment known in the art including a stirred, back-mix, or plug flow reactor.
- the condensable materials from stream 24 (now stream 26) are separated in vessel 70 from the noncondensable light gases stream 28.
- the light gases 28 may be directed to further scrubbing action to remove any condensable iodide and methyl acetate therefrom.
- Condensable material including a major amount of methyl iodide and smaller amounts of acetaldehyde and methyl acetate are directed for the further processing of this invention to remove the acetaldehyde and other carbonyl compounds therefrom.
- streams containing carbonyl impurities may be directed to the tower 72 and then to the reactor 74, or the tower 72 may be bypassed and streams be directed solely to the reactor 74.
- Streams may be combined or fed individually into either the tower or the reactor.
- HAS and sodium hydroxide are added for treatment of the carbonyl impurities via line 54.
- the condensed material of stream 26 is combined with slip stream 34 (the combined stream illustrated in figure 2 as stream 36) and is directed to tower 72.
- stream 36 is then contacted with an amino compound via line 54 and directed to reactor 74. and further processed.
- each stream may be fed individually to tower 72 and processed further. reacted with a compound which converts the carbonyl impurities to derivatives which can be separated from the reaction product by distillation to provide a recycle stream free from carbonyl impurities.
- the methyl iodide-rich phase is treated with an aqueous amino compound. A subsequent separation is carried out to remove the volatile overhead from the 5 non-volatile amine residues.
- the vent gas stream 24 from overhead receiver decanter 22 contains a substantially higher concentration of carbonyl compounds relative to the methyl iodide-rich phase 30; carbonyl compounds such as acetaldehyde.
- carbonyl compounds such as acetaldehyde.
- heavy phase 30 was treated to remove carbonyl compounds by the process set forth in EP 487,284.
- the higher concentration of carbonyl impurities in the vent gas condensate was not recognized. Accordingly, the treatment disclosed in EP 487.284 did not take advantage of the higher concentration of carbonyls in the vent gas condensate stream.
- vent gas is removed via line 24.
- the vent gas includes noncondensable light gases such as carbon monoxide, carbon dioxide, methane, hydrogen as well as condensable materials such as methyl iodide, methyl acetate and carbonyl materials including acetaldehyde.
- the gases are vented from receiver 22 via line 24 and chilled to a temperature sufficient to condense and separate the condensable methyl iodide, methyl acetate, acetaldehyde and o other carbonyl components and directed to vessel 70 shown in Figure 2.
- stream 24 contains a highly concentrated level of acetaldehyde relative to the heavy phase stream 30. For example, it has been found that stream 24 contains approximately 1.3 wt % acetaldehyde whereas stream 30 contains approximately 0.5% acetaldehyde. Typically, the volume of stream 24 is less than about 10 vol % ofthe heavy phase 30 being treated for carbonyl compound removal. 5 Thus, in one aspect of this invention, the condensable stream 24 is directed to processing to remove the carbonyl compounds therefrom.
- Leaving overhead receiver decanter 22 is also the heavy phase stream 30.
- a slip steam 34 generally a small amount, e.g., less than about 25 vol %, preferably, less than about 20 vol %, of heavy phase 30 may also be directed to the carbonyl 0 treatment process of this invention and the remainder recycled to the reactor via line 21.
- the light phase 32 separated in overhead receiver decanter 22 is recycled to the reactor via line 21.
- condensable material from stream 24 and stream 34 may be combined and treated to remove carbonyl compounds therefrom. 12 contained in stream 26.
- the amount of carbonyl impurities can be determined by analytical methods prior to reaction with an amino compound.
- the base used to liberate the free hydroxyl amine may be stored in a tank illustrated in figure 2. and dispersed as necessary via stream 44. It is preferably used in an amount of about 0.8 to about 1.0 equivalents per equivalent of starting hydroxylamine so that a small amount of hydroxylamine remains in the form of its acid salt to create a pH buffer.
- the pH of the reactant solution is maintained in the range of about 4.0 to about 7.0, preferably about 4.0 to about 6.0, and most preferably in the range of about 4.5 to about 5.5.
- Use of larger amounts of base can cause the pH to rise above 7 and result in the decomposition ofthe unstable hydroxylamine free base.
- the free base decomposes to undesirable volatile by-products such as ammonia.
- the reaction is generally run at a temperature of about 0° to about 70°C for a period of from about 1 min. to about 1 hour.
- the circulating reaction lines for examples lines 48 and 54, generally need some form of temperature control to avoid crystallization in the lines.
- Sufficient water is maintained in the reaction process to keep the salts and oximes in solution.
- the water may be supplied by various means. For example, (1) water may be supplied in the HAS itself, by utilizing a dilute HAS solution, e.g. about 10%, (2) by supplying fresh water to the reaction system, (3) by use of recycled water from the reaction process, or (4) by employing dilute NaOH.
- aqueous hydroxylamine salt such as HAS, hydroxylamine hydrochloride, hydroxylamine bisulfate, hydroxylamine acetate, or hydroxylamine phosphate, or the free base form of hydroxylamine is the preferred amino compound for use in the process of this invention
- other amino compounds free base amines or acid salts thereof
- These amino compounds o include but are not limited to aniline and acid salts thereof such as aniline acetate, aniline sulphate, hydrazine, phenylhydrazine and/or their acid salts; alkyl amines such as methylamine, ethylamine. propylamine, phenylamine and naphthylamine.
- other compounds can be used to treat the splitter column overhead, stream 20. including bisulfite salts, as 26+34 TO REACTOR (NO TOWER)
- An alternate process involves directing stream 36 to reactor 74 via line 35 (bypassing tower
- streams 26 and 34 may be individually fed to reactor 74.
- Another alternate process involves directing stream 34 (no combining with stream 26) to tower 72 for alkane and acetic acid removal, and then contact with an aqueous amino compound as 0 described above and further processed.
- Yet another alternate process involves bypassing tower 72 and directing stream 34. via line 35, to reactor 74.
- the stream is then treated with an aqueous amino compound as described and further s processed.
- Still another alternative process involves directing stream 26 only (no combining with stream 34) to tower 72 and then to treatment with an aqueous amino compound as described above and o further processed.
- a still further alternate process of the present invention involves directing stream 26 only
- stream 34 may be processed in column 72 and the distillate combined with stream 26 to be processed as above.
- the HAS may be stored in a tank as illustrated and dispersed as necessary via stream 42. Since hydroxylamine as the free base slowly decomposes, it is preferred to use hydroxylamine in its acid salt form. The free hydroxylamine is liberated upon treatment ofthe acid salt with a base such as 0 potassium hydroxide, sodium hydroxide or lithium hydroxide. If sodium hydroxide is used as the base to liberate the hydroxylamine from its acidic salt, then such liberation also produces the corresponding sodium salt as a byproduct.
- the HAS is preferably used in an amount of about 1 to about 2 equivalents of starting hydroxylamine per equivalent of the carbonyl impurities which are 14 distillation tower 78 to recover methyl iodide.
- a distillate containing a purified methyl iodide recycle stream leaves the tower via line 64. This light ends stream 64 may be recycled to the carbonylation process.
- the bottoms 66 from distillation tower 78 comprise primarily water, the separated oximes, sodium sulfate, unreacted HAS. as well as minor amounts of other impurities such as high boiling point alkanes. Water from a portion of stream 66 may be recycled in the system to preserve water balance.
- oximes such as those formed by reaction of the hydroxylamine and aldehydes, in particular, acetaldehyde oxime can readily convert to the nitrile, e.g., acetonitrile, which has a boiling point close to the methyl iodide-rich recycle 64 and which will distill with and contaminate the recycle phase distillate 64 leaving distillation tower 78.
- nitrile e.g., acetonitrile
- Such conversion occurs more readily under conditions of high temperature. Accordingly, methods to reduce oximes and nitriles are employed. For example, in order to remove oximes and prevent formation of nitriles from distillate 64 leaving distillation tower 78, additional water may be added to the distillation tower 78.
- the water content is preferably in an amount of about 0.1 to about 3 feed volume ratio of water to organic phase 52 (tower) feed. The water partitions the oxime to the bottom of distillation tower 78, and reduces the temperature needed for distillation, further reducing the undesirable nitrile formation.
- reaction of hydroxylamine with carbonyl impurities yields an oxime whereas reaction with hydrazine yields the hydrazone.
- nitrile formation from the reaction product of an aldehyde with an amino compound can result during prolonged heating such as during distillation.
- the nitrile forming reactions are shown below for (1 ) oxime products and (2) hydrazone products.
- R — C NOH ⁇ RC ⁇ N + H 2 0 (1)
- the light aqueous phase 54 which contains unreacted hydroxylamine sulfate as well as most of the oximation products from reaction of the carbonyl impurities with the hydroxylamine is separated.
- the aqueous phase containing the hydroxylamine sulfate may be fully or partially recycled to reactor 74 via line 54.
- a portion of stream 54 illustrated as stream 58 may be directed to distillation tower 78 for stripping ofthe methyl iodide.
- the oximes concentrate in the aqueous phase such that a purge ofthe formed oximes is necessary. These may be purged directly via stream 59 or purged and fed through stream 58 to recover soluble methyl iodide.
- the recirculation ofthe aqueous phase 54 greatly improves pH control which is necessary to release the hydroxylamine from the hydroxylamine salt and allows optimum reaction with the carbonyl impurities.
- the organic phase 52 containing methyl iodide, minor amounts of water, as well as trace amounts of hydroxylamine sulfate. oximes and impurities which separate from the aqueous hydroxylamine sulfate phase 54 is withdrawn from the decanter 76 via line 52 and directed to 16
- hydroxylamine acid salt is selected from the group consisting of hydroxylamine sulfate, hydroxylamine hydrochloride, hydroxylamine bisulfate, hydroxylamine acetate, hydroxylamine phosphate, or the free base form of hydroxylamine.
- the amino compound is selected from the group consisting of aniline acetate, aniline sulphate, hydrazine, phenylhydrazine, methylamine, ethylamine, propylamine, phenylamine, naphthylamine, and acid salts thereof.
- the base is selected from the group consisting of sodium hydroxide, potassium hydroxide, and lithium hydroxide.
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Engineering & Computer Science (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- General Chemical & Material Sciences (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Applications Claiming Priority (3)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
US08/526,338 US5783731A (en) | 1995-09-11 | 1995-09-11 | Removal of carbonyl impurities from a carbonylation process stream |
US526338 | 1995-09-11 | ||
PCT/US1996/014436 WO1997010198A1 (en) | 1995-09-11 | 1996-09-06 | Removal of carbonyl impurities from a carbonylation process stream |
Publications (2)
Publication Number | Publication Date |
---|---|
EP0932595A1 true EP0932595A1 (de) | 1999-08-04 |
EP0932595B1 EP0932595B1 (de) | 2001-12-12 |
Family
ID=24096923
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
EP96932977A Expired - Lifetime EP0932595B1 (de) | 1995-09-11 | 1996-09-06 | Entfernung von carbonylverunreinigungen aus einem carbonylierungsverfahrensstrom |
Country Status (12)
Country | Link |
---|---|
US (1) | US5783731A (de) |
EP (1) | EP0932595B1 (de) |
JP (1) | JP3914263B2 (de) |
KR (1) | KR100450813B1 (de) |
CN (1) | CN1077096C (de) |
BR (1) | BR9610326A (de) |
CA (1) | CA2230946C (de) |
CZ (1) | CZ292740B6 (de) |
DE (1) | DE69618027T2 (de) |
ES (1) | ES2167604T3 (de) |
TW (1) | TW386990B (de) |
WO (1) | WO1997010198A1 (de) |
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US6552221B1 (en) | 1998-12-18 | 2003-04-22 | Millenium Petrochemicals, Inc. | Process control for acetic acid manufacture |
US6251256B1 (en) | 1999-02-04 | 2001-06-26 | Celanese International Corporation | Process for electrochemical oxidation of an aldehyde to an ester |
TW562149U (en) * | 2003-03-06 | 2003-11-11 | Benq Corp | A projector with a flexible sheet to reduce electromagnetic interference |
CN100430363C (zh) * | 2003-10-30 | 2008-11-05 | 上海吴泾化工有限公司 | 一种羰基化生产醋酸的改进方法及其装置 |
US7271293B2 (en) * | 2004-03-02 | 2007-09-18 | Celanese International Corporation | Control method for process of removing permanganate reducing compounds from methanol carbonylation process |
US7208624B2 (en) * | 2004-03-02 | 2007-04-24 | Celanese International Corporation | Process for producing acetic acid |
US7223883B2 (en) * | 2004-03-02 | 2007-05-29 | Celanese International Corporation | Removal of permanganate reducing compounds from methanol carbonylation process stream |
US7223886B2 (en) * | 2004-03-02 | 2007-05-29 | Celanese International Corporation | Removal of permanganate reducing compounds from methanol carbonylation process stream |
US7855306B2 (en) | 2005-04-28 | 2010-12-21 | Celanese International Corporation | Process for the production of acetic acid |
JP5486299B2 (ja) * | 2006-04-14 | 2014-05-07 | セラニーズ・インターナショナル・コーポレーション | 標的ストリーム中のアルデヒド濃度の低減法 |
US7524988B2 (en) * | 2006-08-01 | 2009-04-28 | Lyondell Chemical Technology, L.P. | Preparation of acetic acid |
US7208625B1 (en) | 2006-08-04 | 2007-04-24 | Lyondell Chemical Technology, L.P. | Removing permanganate-reducing impurities from acetic acid |
US7485749B2 (en) * | 2006-08-22 | 2009-02-03 | Lyondell Chemical Technology, L.P. | Preparation of acetic acid |
US7902397B2 (en) * | 2007-10-11 | 2011-03-08 | Celanese International Corporation | Method and apparatus for making acetic acid with improved productivity |
US7790920B2 (en) * | 2008-09-11 | 2010-09-07 | Lyondell Chemical Technology, L.P. | Preparation of acetic acid |
US8685256B2 (en) * | 2010-12-21 | 2014-04-01 | Cytec Technology Corp. | Microdispersions of hydroxamated polymers and methods of making and using them |
US9090554B2 (en) | 2011-12-21 | 2015-07-28 | Lyondellbasell Acetyls, Llc | Process for the manufacture of acetic acid |
CA2859068C (en) | 2011-12-21 | 2016-08-16 | Equistar Chemicals, Lp | Process for the manufacture of acetic acid |
US9051258B2 (en) | 2011-12-21 | 2015-06-09 | Lyondellbasell Acetyls, Llc | Process for the manufacture of acetic acid |
US9776941B2 (en) | 2012-12-21 | 2017-10-03 | Daicel Corporation | Process for producing acetic acid |
US9260369B1 (en) | 2014-11-14 | 2016-02-16 | Celanese International Corporation | Processes for producing acetic acid product having low butyl acetate content |
US9302975B1 (en) | 2015-07-01 | 2016-04-05 | Celanese International Corporation | Process for flashing a reaction medium |
EP3277655A1 (de) * | 2015-03-31 | 2018-02-07 | SABIC Global Technologies B.V. | Verfahren zur reinigung einer aromatischen disäure oder der entsprechenden anhydride |
US20180079705A1 (en) * | 2015-03-31 | 2018-03-22 | Sabic Global Technologies B.V. | Method for purification of an aromatic diacid or the corresponding anhydride |
KR102438920B1 (ko) | 2015-10-02 | 2022-08-31 | 셀라니즈 인터내셔날 코포레이션 | 물의 재순환과 함께 아세트산을 생산하는 방법 |
CN110872223B (zh) * | 2018-09-04 | 2024-08-27 | 河南顺达新能源科技有限公司 | 一种脱除醋酸中乙醛杂质的装置 |
WO2023158791A1 (en) * | 2022-02-18 | 2023-08-24 | Lyondellbasell Acetyls, Llc | Removal of aldehydes in acetic acid production |
WO2023225077A1 (en) | 2022-05-19 | 2023-11-23 | Lyondellbasell Acetyls, Llc | Methods for improved control of glacial acetic acid processes |
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AU8790391A (en) * | 1990-11-19 | 1992-05-21 | Hoechst Celanese Corporation | Removal of carbonyl impurities from a carbonylation process stream |
JPH04184788A (ja) * | 1990-11-20 | 1992-07-01 | Fujitsu Ltd | 半導体記憶装置 |
AU639630B2 (en) * | 1991-01-28 | 1993-07-29 | Celanese International Corporation | Removal of carbonyl impurities from carbonylation process stream |
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1995
- 1995-09-11 US US08/526,338 patent/US5783731A/en not_active Expired - Lifetime
-
1996
- 1996-09-06 KR KR10-1998-0701784A patent/KR100450813B1/ko not_active IP Right Cessation
- 1996-09-06 ES ES96932977T patent/ES2167604T3/es not_active Expired - Lifetime
- 1996-09-06 EP EP96932977A patent/EP0932595B1/de not_active Expired - Lifetime
- 1996-09-06 CN CN96196884A patent/CN1077096C/zh not_active Expired - Fee Related
- 1996-09-06 CZ CZ1998716A patent/CZ292740B6/cs not_active IP Right Cessation
- 1996-09-06 JP JP51202897A patent/JP3914263B2/ja not_active Expired - Fee Related
- 1996-09-06 BR BR9610326-4A patent/BR9610326A/pt not_active Application Discontinuation
- 1996-09-06 WO PCT/US1996/014436 patent/WO1997010198A1/en active IP Right Grant
- 1996-09-06 DE DE69618027T patent/DE69618027T2/de not_active Expired - Lifetime
- 1996-09-06 CA CA002230946A patent/CA2230946C/en not_active Expired - Fee Related
- 1996-10-05 TW TW085112191A patent/TW386990B/zh not_active IP Right Cessation
Non-Patent Citations (1)
Title |
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See references of WO9710198A1 * |
Also Published As
Publication number | Publication date |
---|---|
KR19990044536A (ko) | 1999-06-25 |
CZ292740B6 (cs) | 2003-12-17 |
EP0932595B1 (de) | 2001-12-12 |
MX9801900A (es) | 1998-05-31 |
DE69618027T2 (de) | 2002-10-02 |
DE69618027D1 (de) | 2002-01-24 |
CN1077096C (zh) | 2002-01-02 |
CA2230946C (en) | 2007-01-09 |
US5783731A (en) | 1998-07-21 |
WO1997010198A1 (en) | 1997-03-20 |
JP3914263B2 (ja) | 2007-05-16 |
TW386990B (en) | 2000-04-11 |
ES2167604T3 (es) | 2002-05-16 |
CZ71698A3 (cs) | 1998-06-17 |
BR9610326A (pt) | 2000-10-24 |
CA2230946A1 (en) | 1997-03-20 |
KR100450813B1 (ko) | 2004-11-16 |
JPH11512431A (ja) | 1999-10-26 |
CN1196042A (zh) | 1998-10-14 |
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